JP3251015B2 - Silicone oil-based aqueous dispersion that can be crosslinked when water is removed - Google Patents

Abstract

Aqueous dispersions containing: a silicone oil (A) which is cross-linkable by condensation, optionally in the presence of a cross-linking agent (B), into an elastomer; optionally a cross-linking agent (B), a silane (C) and a mineral filler (D); and a catalytic amount of a hardening compound (E). Said dispersions are characterized in that they are produced by kneading a mixture of (1) a silicone phase (F) with a viscosity of at least 3 Pas, containing the oil (A) and optionally one or more of components (B), (C), (D) or (E), and 2) an aqueous phase comprising water and at least one surfactant (G), wherein the weight ratio water/water + surfactant(s) is such that the viscosity of the aqueous phase is preferably at least as high as that of the silicone phase (F); for a sufficient time and with sufficient shear to give an oil-in-water emulsion having a particle size of 0.1-5 micrometres; and optionally by diluting with water until a 25-97 % dry extract is obtained; followed by adding the component(s) not present in the silicone phase (F).

Description

The present invention relates to novel viscous silicone oil-based aqueous dispersions which can crosslink to elastomers upon removal of water, a process for their preparation and silicone elastomer products or coatings for the building industry, in particular seals To their use in the production of materials, paints and the like.

A crosslinking agent (in particular, colloidal silica, alkali metal silicate, polyalkoxysilane, polyalkenyloxysilane, polyacyloxysilane, polyketiminoxysilane, polyamino or polyamidesilane, isocyanate, polysilicate, Silsesquioxane resin, hydroxylated,
It is known that the incorporation of an alkoxylated or acyloxylated reactive silicone resin type) makes it possible to obtain, after the incorporation of the filler and the organometallic catalyst, a dispersion which can be crosslinked to the elastomer upon removal of water. (US Patent 42
21688, 4244849, 3355406, 3294725, 458434
1, 4618642, 4608412, 4554187, European patent
266729, 332544, 304719, 365439, French patent
2642765, 2637606, 2638166).

To obtain an aqueous emulsion of a hydroxylated silicone oil, it is possible to start with a pre-polymerized hydroxylated oil, make it an aqueous emulsion and stabilize the emulsion with anionic and / or nonionic surfactants. Known (French Patents 2064563, 2
114230, 2094322 and European Patent 169098). Conventional methods (using colloid mills, homogenizers or similar types of equipment) are limited to emulsifying polymers having a viscosity of less than about 500 mPa s. More viscous oils can only be emulsified with marginal success but at the expense of particle size and therefore the stability of the emulsion obtained (particle size is very coarse, less than 1 μm). Is much larger). The reason for this is that the emulsions of reactive silicone oils used are generally low molecular weight cyclic or linear oligomers (these use anionic surfactants which act in a conventional manner, ie preferably also as polymerization catalysts). (Easily emulsified by the method described in US Pat. Nos. 3,247,725 and 3,334,091).

According to the teachings of U.S. Pat. No. 4,608,412, dispersions of very high molecular weight (Mw> 200,000) before and after storing the dispersion in a sealed cartridge to obtain a sealant having good mechanical properties, especially a high elongation at break. The required polymer is required. According to this method, the aqueous dispersion is obtained by emulsion polymerization in the presence of an ionic (most often anionic) surfactant, which impairs the stability of the sealant and its performance (Adhesiveness, mechanical properties, etc.).

Here, we believe that storage is stable (because it is prepared from an aqueous emulsion of silicone oil of fine particle size and cannot contain any anionic surfactant), and that it is highly mechanical on removal of water. Α, ω-functional viscous silicone oil-based aqueous dispersions have been found which can be crosslinked to elastomers of specific properties. In addition, these dispersions have the advantage of containing a high concentration of dispersed silicone polymer with a well controlled degree of polymerization (compared to that of the polymer obtained by emulsion polymerization). .

According to the invention, these include: at least one organopolysiloxane oil (A), which can optionally be crosslinked to an elastomer by condensation in the presence of a crosslinking agent (B); 0.1 to 100 parts by weight, preferably 0.5 to 30 parts by weight, of at least one crosslinking agent (B); optionally at least 50 parts by weight, preferably up to 10 parts by weight, per 100 parts by weight of oil (A) One silane (C), optionally, up to 300 parts by weight, preferably 3 to 100 parts by weight, of a siliceous and / or non-siliceous inorganic filler (D) per 100 parts by weight of oil (A), and An aqueous dispersion comprising a catalytically effective amount of a curing catalyst compound (E), and a silicone phase (F) having a kinematic viscosity at 25 ° C. of at least 3 Pas, preferably of the order of 50-1000 Pas. , Oil (A) or a mixture of oil (A) and 100 parts by weight of a silicone phase (F) containing at least one of the components (B), (C), (D) and (E) as an active ingredient, and at least one preferably nonionic surfactant (G) (HL of such a surfactant or mixture of surfactants)
B is at least 10 and preferably between 10 and 15) 3 to 20
Parts by weight, preferably 5 to 15 parts by weight, 2 to 20 parts by weight of water, preferably 3 to 15 parts by weight, and the weight ratio of water / water + surfactant is water + surfactant The mixture is such that the viscosity of the mixture of agents is such that it is half or more than that of the silicone phase (F) and preferably such that the viscosity of the silicone phase (F) is or higher. Kneading for a period and under shearing conditions sufficient to obtain an "oil / water" emulsion having a particle size of about 5 μm, preferably about 0.2 to 2 μm;
Then optionally diluting with water until a solids content of 25-97%, preferably higher than 70%, is obtained, and adding components not present in the silicone phase (F). Aqueous dispersion.

For the good practice of the present invention, the measurement of the kinematic viscosity of the silicone phase (F) is described, for example, in the AFNOR NFT standard 7
6 can be carried out with the help of a Brookfield viscometer according to 102.

Oil (A) is an α, ω-hydroxylated oil or a functional oil that optionally contains at least two functional groups per molecule that can be condensed after hydrolysis. These are represented by the general formula (I) Wherein a is 0 or 1; b is 0 or 1; a + b = 0, 1 or 2, n is sufficient to give the desired viscosity of the polymer of formula (A) R groups are the same or different and OH groups (when a + b = 2) alkoxy or alkenyloxy groups containing 1 to 10 carbon atoms, 6 to 13 carbon atoms An aryloxy group containing 1 to 13 carbon atoms, an acyloxy group containing 1 to 13 carbon atoms, a ketiminoxy group containing 1 to 8 carbon atoms, 1 to 6 carbon atoms bonded to silicon by a Si-N bond. Wherein the R ¹ and R ² groups are the same or different and are an alkyl or alkenyl aliphatic group containing 1 to 10 carbon atoms or a phenyl aromatic group. And such a group is a halogen atom or a Optionally substituted by ano groups, at least 80% of which represent methyl groups; R ³ and R ⁴ groups being the same or different and containing 1 to 13 carbon atoms, alkyl, amino Represents an organic group which is an alkyl, polyaminoalkyl, epoxyalkyl or alkenyl aliphatic group or an arylaromatic group containing 6 to 13 carbon atoms, and optionally contains at least 2 functional groups capable of condensation after hydrolysis per molecule. Preferably at least three, but preferably at least 80% of the R ^{1 to} R ⁴ groups represent a methyl group].

Examples of the R group include alkoxy such as methoxy, ethoxy and octyloxy, alkenyloxy such as vinyloxy, hexenyloxy and isopropenyloxy, aryloxy such as phenoxy, acyloxy such as acetoxy, and ON = C (CH ₃ ) C _2. H ₅ etc. Kechiminokishi, ethylamino, amino functional group such as phenylamino, may be mentioned amide functional group such as a methyl acetamide.

For the above aliphatic or aromatic organic groups, R ¹ ,
R ² is a group such as methyl, ethyl, octyl, trifluoropropyl, vinyl, and phenyl; R ³ and R ⁴ are
Methyl, ethyl, octyl, vinyl, allyl, groups such as _{phenyl, - (CH 2) 3 -NH} 2, - (CH 2) 3 -NH- (CH 2)
_2- NH _{2 and the} like can be mentioned.

Specific examples of the R ¹ R ² SiO unit present in the oil (A) include (CH ₃ ) ₂ SiO, CH ₃ (CH ₂ CHCH) SiO, and CH ₃ (C ₆ H ₅ ) S
iO, (C ₆ H ₅ ) ₂ SiO and the like can be mentioned.

A specific example of the RR ₃ R ₄ SiO unit is (CH ₃ ) ₂ (O
_{H) SiO, (OCH 3)} 3 SiO, [O-C (CH 3) = CH 2] 3 SiO,
_{[ON = C (CH 3)} ] 3 SiO, (NH-CH 3) 3 SiO, (NH-CO-
CH ₃ ) ₃ SiO and the like.

When the oil (A) is an α, ω- (dihydroxy) polydiorganosiloxane polymer, a crosslinking agent (B) must be used. Numerous crosslinkers can be used, depending on the amount being a function of the properties. These are well known to those skilled in the art.

An example of the cross-linking agent is described together with a preferred amount expressed as parts per 100 parts by weight of the oil (A): 0.1 to 10 parts of colloidal silica, 0.5 to 10 parts of sodium silicate, silica powder (pyrogenic or precipitated silica). ) 1 to 15 parts, alkali metal organosilicate (European Patent 266729) 0.1
1 to 100 parts of a microemulsion of silsesquioxane resin (US Pat. Nos. 3,355,406 and 3,433,780); 5 to 100 parts of a low molecular weight reactive silicone resin containing alkoxy and acyloxy groups (US Pat. No. 4,554,187); the molecular weight of the toluene-insoluble silicone resin (European Patent 304,719) 5-100 parts, wherein R _'3 SiO _0.5 (M) and / or R' ₂ units of formula R'SiO _1.5 of SiO (D) (T) and / or SiO ₂ combinations (wherein, R 'is primarily C ₁ -C ₆ alkyl, vinyl and 3,3,3 trifluoropropyl propyl group) with units of (Q) from consisting hydroxylated silicone resin (0.1% to 10% 5 to 100 parts (weight of hydroxyl group of these resins) (among these resins, mention may in particular be made of MQ, MDQ, TDM and TD resins (French Patent 2638166)), formula (R ") _u SiX _{(4-u )} (wherein, R "is a monovalent organic group, especially methyl or vinyl Wherein u is 1 or 0 and X is an organic condensable and / or hydrolysable group having the same definition as the R group in formula (I) above (especially U.S. Pat.
3294725, 4584341, 4686442, 4608412, 4525565, European Patents 387157, 340120, 364375, 1248826 and French Patent 1.23477, alkoxy, alkenyloxy, acyloxy, ketiminoxy, alkylamino, alkylamidosilane) 1 to 20 parts .

As an example, the following alkoxysilane: Si (OC ₂ H
₅ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₂ H ₅ ) ₃ , (C ₂ H
₅ O) ₃ Si (OCH ₃ ), CH ₂ CHCHSi (OCH ₃ ) ₃ , CH ₃ (CH ₂ CC
H) Si (OCH ₃ ) ₂ , CH ₂ CHCH (OC ₂ H ₅ ) ₃ , CH ₂ CHCHSi [ON
ＣC (CH ₃ ) C ₂ H ₅ ], CH ₃ Si [ON ＝ C (CH ₃ ) ₂ ] ₃ and C
_{H 3 Si [-C (CH 3} ) = C 2] 3, and methyltri (N-
Methylacetamidosilane), methyltri (cyclohexylaminosilane) and the like.

The silane (C) optionally present in the composition of the dispersion of the invention is a by-product of the hydrolysis of the oil (A) as well as the silicone elastomer composition obtained after crosslinking of the dispersion which constitutes the subject of the invention It may be an additive that makes it possible to modify the physicochemical properties of the compound.

The silane which is a by-product of the hydrolysis reaction of the oil (A) is represented by the formula (R ⁵ ) _c Si (R) _4-c [wherein c is 0, 1 or 2, and R ⁵ is the same. Or a heterogeneous oil (A) of the formula (I)
R groups correspond to the groups R ³ and R ⁴ , wherein the R group is a polyorganosiloxane oil of formula (I) (A)
Corresponding to the organic group R].
An example of such a silane is the above-mentioned silane for crosslinking. They are generally present in amounts of from about 0 to 10 parts by weight and preferably of from about 0 to 5 parts by weight per 100 parts by weight of oil (A).

The additive silane that modifies the physicochemical properties may be, in particular, an adhesion promoter such as those described in EP 340120. Particularly, aminopropyltriethyloxysilane, aminopropylmethyldiethoxysilane, glycidyloxypropyltrimethoxysilane and the like can be mentioned. These are used in amounts ranging up to 50% by weight of the oil (A) and generally in amounts of 0.5 to 10%.

Examples of the siliceous filler (D) are reinforcing fillers such as colloidal silica, pyrogenic or precipitated silica powder, and semi-reinforcing silicas such as diatomaceous earth and crushed quartz. , Is not selected as a crosslinking agent (B). Examples of non-silicate fillers include natural calcium carbonate, hydrated alumina, magnesium hydroxide, carbon black,
Titanium dioxide, aluminum oxide, vermiculite, zinc oxide, mica, talc, iron oxide, barium sulfate, slaked lime, and the like.
The particle size of these fillers is generally about 0.001 to 300 μm.

Curing catalyst compounds (E) are well known to those skilled in the art. These are lead, zinc, zirconium, titanium, iron, barium,
Carboxylates or halides of metals such as calcium, manganese etc. and especially tin. For example,
The reaction product of tin dicarboxylate with ethyl polysilicate (US Pat. No. 3,682,919), the reaction product of dibutyltin diacetate with alkyl silicate or alkyl trialkoxysilane (Belgian patent 842305), tin bisquilate (European patent 147323 and 235049) and diorganotin dicarboxylate (GB 1289900). These are about 3 per 100 parts by weight of oil (A).
In good amounts and preferably up to parts by weight
It can be used in an amount of 0.05 to 1 part by weight.

The surfactant used is preferably non-ionic. Examples include alkoxylated fatty acids, polyalkoxylated alkyl phenols, polyalkoxylated fatty alcohols, polyalkoxylated or polyglycerolated fatty amides, polyglycerolated alcohols and α-diols, ethylene oxide-propylene oxide block polymers, and the like, as well as alkyl Examples include glucoside, alkyl polyglucoside, sugar ether, sugar ester, sugar glyceride, sorbitan ester, and the like, and ethoxylated compounds of these sugar derivatives.

The anionic surfactant can be selected from alkali metal alkyl benzene sulfonates, alkyl sulfonates, alkyl ether sulfonates, alkyl aryl ether sulfonates, dioctyl sulfosuccinates and the like.

The surfactant (mixture) is selected as a function of the nature of the silicone oil (A) to be emulsified. α, ω
In order to emulsify a silicone oil (A) comprising a bis (hydroxy) polydimethylsiloxane polymer,
An HLB value of about 11 to 15 is selected.

The weight ratio of water / water + surfactant is silicone phase (F)
And the properties of the surfactant (mixture). This ratio stabilizes, for example, an emulsion of a silicone phase consisting of an .alpha.,. Omega.-dihydroxylated oil having a viscosity of the order of 30 to 500 Pas, with nonylphenol containing 9 or 10 ethoxy units as sole surfactant. About 20 / 100-70 / 100 and preferably 25/1
It is about 00-60 / 100.

The silicone phase (F), which is made into an "oil / water type" emulsion by kneading in the presence of water and at least one surfactant, has (F1) a viscosity of at least 3 Pas, preferably of the order of 50 to 1000 Pas. Oil (A), (F2) a mixture of oils (A) having a viscosity of at least about 3 Pa s, preferably about 50 to 1000 Pa s, and (F3) at least one having a viscosity of at least about 3 Pa s, preferably about 50 to 1000 Pa s. A mixture of oil (A) and at least one crosslinking agent (B) (if necessary) and / or silane (C) and / or at least one filler (D), (F4) as an optional component At least one silane (C)
And / or a mixture of at least one oil (A) and a catalyst compound (E) in the presence of at least one filler (D).

"Oil / water" emulsification of the silicone phase may be accomplished by introducing the silicone phase into a mixture of water + surfactant or, preferably, by introducing water into the mixture of silicone phase + surfactant and on the order of 10-50 ° C. The temperature is adjusted by kneading.

Conventional kneading devices, in particular warm stirring devices, can be used. Thus, the kneading operation is performed when the movable member has 2500 rotations /
Min or more (preferably 1500 rpm / min and especially 500 rpm
(Kilometers / min or more) and a kneader equipped with a stirrer with a tangential velocity at the end of the movable member not exceeding 20 m / s (preferably 5 m / s, especially 2.5 m / s). it can. Advantageously, the ratio of the tangential speed at the end of the movable member relative to the distance between the end portion and the kneader wall of the movable member, 50000S ^- preferably 10000s ¹ particularly less than 2500 s ^1.

Examples include single or multiple screw, planetary mixers, hook mixers, slow dispersers, static mixers, and blades, propellers, anchors and similar mixers.

After the optional dilution of the mixture, the components of the dispersion of the invention which are not present in the "oil / water" emulsion thus prepared, ie in the case of emulsions of the silicone phase (F1), (F2) or (F3) Are the catalyst compound, preferably in the form of an aqueous emulsion, and other optional components not present in the phase; in the case of an emulsion of the silicone phase (F4), the crosslinking agent (B) (if necessary) and Other optional components, which are not present in, are introduced and dispersed in the mixture. This takes place by kneading in a kneader of the same type as described above and preferably in the one used for the emulsification.

The dispersion which constitutes the subject of the present invention further comprises other additives, for example plasticizers used in an amount of 0 to 70 parts by weight per 100 parts by weight of oil (A), for example of the order of 300 to 10,000 mPa s Polydimethylsiloxane oil having a viscosity of, dioctyl phthalate,
Dialkylbenzenes and the like (optionally in the form of an aqueous emulsion); thickeners used in amounts which can range up to 10% by weight of the final aqueous dispersion, for example alkali metal polyacrylates, polyvinyl alcohol, polyethylene Water-soluble polymers with a molecular weight of more than 10,000 g / mol, such as glycols, polyvinylpyrrolidone, carrageenan, alginate, methylcellulose, hydroxyalkylcellulose, xanthan gum, etc.-an amount which can range up to 10% by weight of the final aqueous dispersion The filler-dispersant used in the above can be included, for example, alkali metal polyacrylates having a molecular weight of less than 5000, inorganic phosphates, and the like. These additives can be introduced into either the silicone phase before emulsification or the emulsion before dilution.

The various components in the dispersion according to the invention are present in such an amount that the solids content is higher than 40% and generally of the order of 70 to 97%. pH is adjusted to between 4 and 13 by adding organic or inorganic acids or bases (potassium hydroxide, amines, etc.).

The final dispersion obtained is homogenized and then degassed. It is then packaged in a packaging material that is impermeable to air and water vapor.

The dispersion constituting the object of the present invention can be used for the production of elastomer paints, chemicals for imparting water repellency to surface materials, sealing materials, flame-retardant elastomer products and the like.

The following examples are provided as examples of the invention, but should not be construed as limiting the scope and concept of the invention.

Example 1 Preparation of an emulsion of silicone phase (F) consisting of hydroxylated oil (A) 5 liter arm kneader of the type "Kustner" (K
ustner) and 1500 g of an α, ω-bis (hydroxy) polydimethylsiloxane oil having a viscosity of 175 Pas (trade name “48V175000”).
oil ”), followed by 75 g of the trade name“ Cemulsol NP ”showing an HLB of 12.8.
9 "(nonylphenol containing 9 ethoxy units, sold by the company Rh ロ ー ne Poulin).

The mixture is stirred at 90 rpm for 15 minutes. Then 100g
Of water is gradually poured in over about 10 minutes with the same stirring, and the mixture is further kneaded for about 150 minutes with the same stirring. The weight ratio of water / water + surfactant is 0.57 (the kinematic viscosity of this surfactant / water mixture is 380 pas at a shear rate of 1 s ^-1 ). The resulting emulsion has a particle size of 375 nm. It is then diluted with 584 g of water to give a solids content of 70%.

Preparation of Aqueous Dispersion and Water Sealant To 429 g of the diluted emulsion thus obtained is: 6.6 g of an aqueous solution containing 50% potassium hydroxide (KOH), and 1.56 containing 38% by weight of dioctyltin dilaurate.
g of an aqueous emulsion (stabilized with polyvinyl alcohol).

The mixture is homogenized by a turbine for 10 minutes. After transferring this mixture to a 1.6 liter capacity “Meili” arm kneader (commercially available from Meili), 210 g
Of precipitated and coated calcium carbonate (trade name "Winnnofil SP" marketed by ICI). The kneading was carried out for 30 minutes, then containing 2.2% by weight of hydroxyl groups and 70% by weight of _1.5 units of CH ₃ SiO and 30% by weight of (C
21 g of a silicone DT resin consisting of H ₃ ) ₂ SiO units and exhibiting a viscosity of 5400 mPa s are introduced. The dispersion is homogenized by kneading for 30 minutes. It is degassed for 10 minutes with stirring under vacuum and then packaged in a vapor-tight packaging material (polyethylene cartridge). Its pH is around 9.5. This silicone DT resin was manufactured in the following manner. That is, a mixture of methyltrichlorosilane (75 g) and dimethyldichlorosilane (25 g) is gradually poured into a reaction medium composed of water (130 g) and an organic solvent of ether type. The hydrolysis reaction is carried out at 50 ° C. with stirring. The HCl acid formed remains in the aqueous phase. At the end of the reaction, the reaction medium is decanted, then the silicone phase is recovered and treated under vacuum to remove the solvent and to obtain a pure DT silicone resin having the above composition.

After storage at 25 ° C. for 4 days, the dispersion was applied with a doctor blade to form a 2 mm thick film, which was dried at ambient temperature for 7 minutes.
Leave to dry for days.

For the dried coating, the following mechanical properties: Shore A hardness according to ASTM standard D-2240 (SA
H), ・ ASTM standard D-460 corresponding to ASTM standard D-412
Tensile strength in MPa (T / S) according to 02; Elongation at break (E / B) in% according to AFNOR standard T-46002; Elastic modulus in MPa at 100% elongation according to AFNOR standard T-46002 (T / S) M100) and are measured.

The compressibility of the aqueous dispersion against glass or concrete is evaluated by depositing 3-4 mm thick beads on these supports and drying the beads for 2 weeks. At this time, the adhesion is evaluated by pulling the dried beads by hand. The stability of the aqueous dispersion is
The sealed package is evaluated by heat aging in a 50 ° C. oven for 7-14 days. Form a 2mm thick coating,
After leaving it to dry at ambient temperature for 7 days, its mechanical properties are re-examined. Table 1 shows the obtained results.

Example 2 Preparation of an Emulsion of Silicone Phase (F) Consisting of Hydroxylated Oil (A) The procedure of preparing an emulsion of oil (A) described in Example 1 is repeated, except that 1500 g of "48V175000 oil" and 150 g of " Use Cemulsol NP 9 "and add 150g of water to approximately 10
Introduce over a minute.

After 90 minutes of kneading at 90 rpm, a stable emulsion of 380 nm is obtained. It is diluted to a solids content of 75% by adding 555 g of water and remixing for 20 minutes.

Preparation of Aqueous Dispersion and Water Sealant Example 1 Starting with the emulsion of oil (A) prepared above
Is repeated. Table 1 shows the properties of the obtained sealant.

Example 3 Preparation of an Emulsion of the Silicone Phase (F) Consisting of a Hydroxylated Oil (A) In the kneader of Example 1: 1500 g of "48V175000 oil"; 37.5 g of "Cemulsol NP 5" exhibiting an HLB of 10 (Rhone
112.5 g of "Cemulsol NP 12" exhibiting 14 HLB (nonylphenol containing 12 ethoxy units sold by Rhone Poulin) sold by Poulin, Inc. ) And. This mixture of surfactants exhibits an HLB of about 12.

After kneading for 20 minutes at 90 rpm, 100 g of water are added over a period of about 6 minutes. Kneading is carried out for 1 hour under the same conditions. A further 30 g of water are added over about 2 minutes and stirring is continued for 1 hour under the same conditions. The average particle size of the obtained emulsion is 580 nm. The emulsion is adjusted to a solids content of 75% by dilution with 470 g of water.

Preparation of Aqueous Dispersion and Water Sealant In a 1.6 liter capacity "Meili" arm kneader, 471 g of the diluted emulsion prepared above, and an aqueous emulsion containing 37% dioctyltin dilaurate and stabilized with polyvinyl alcohol 1.56
g, and kneading is carried out for 30 minutes. 30 g of α, ω-bis (trimethyl) polydimethylsiloxane having a viscosity of 100 mPa s are added and kneading is carried out for 15 minutes. Example 1
21 g of the silicone DT resin used in step 1 are introduced and kneading is carried out for 20 minutes, then 10 g of an aqueous solution containing 50% of KOH are added. The mixture is homogenized at atmospheric pressure for 20 minutes and under vacuum for 5 minutes to degas the sealant before packaging in cartridges. Table 1 shows the properties of the obtained sealant.

Example 4 Preparation of an Emulsion of Silicone Phase (F) Consisting of Hydroxylated Oil (A) In the kneader of Example 1, 1500 g of "48V175000 oil" HLB = 10 45 g of trade name "Genapol X 050" (Hoechst AG) Ethoxylated fatty alcohols marketed by
A mixture of 45 g of HLB = 15 and a mixture with the trade name "Genapol UD 110" (an ethoxylated fatty alcohol marketed by Hoechst) preheated to 50 ° C. is introduced. This mixture of surfactants has an HLB of about 12.5
Having.

After 20 minutes of kneading at 90 rpm, 105 g of water are introduced over a period of about 6 minutes. By kneading at 90 revolutions / minute, a two-population emulsion is obtained, consisting of 95% by volume of a first population with an average diameter of 785 nm and 5% by volume of a second population with an average diameter of 298 nm. The solids content of the final emulsion is adjusted to 76% by addition of 440 g of water and remixing at 90 rpm for 20 minutes.

Preparation of Aqueous Dispersion and Water Sealant In a 1.6 liter "Meili" arm kneader: 423 g of the above emulsion, 1.56 g of tin dilaurate emulsion, 21 g of trade name "Socal 312 N" calcium carbonate (by Solvay) (Commercially available), 210 g of the DT resin according to Example 1, and 10 g of a solution containing 50% of KOH and 6 g of water are introduced and kneaded for 20 minutes each after the introduction of each of the components of the mixture. . The final dispersion is degassed under vacuum for 5 minutes and packaged in a sealed packaging material. The characteristics are described in Table 1.

Example 5 Preparation of a methoxy-functional oil (A) To the kneader of Example 1, 1500 g of "48V175000 oil" and 15 g of vinyltrimethoxysilane are introduced. After 10 minutes of stirring at 90 rpm, 3.75
7.95 g of methanol solution containing 5% lithium oxide (LiOH.H ₂ O) are added. After stirring for 25 minutes under the same conditions, the mixture is neutralized by adding 6 g of the reaction product of phosphoric acid and octylmethylcyclotetrasiloxane (containing 8.5% of H ₃ PO ₄ ).

Preparation of Silicone Phase (F) Consisting of a Methoxy-Functional Oil (A) To the resulting oil, 75 g of "Cemulsol NP 5" and 75 g of "Cem
Add the mixture with ulsol NP 12 ". The mixture is kneaded at 90 rev / min for 10 minutes, 130 g of water are slowly added over about 8 minutes, and then mixing is carried out at 90 rev / min for 90 minutes. An emulsion with an average particle size of 535 nm is obtained.
Dilute with water.

Preparation of Aqueous Dispersion and Water Sealant Into a 1.6 liter capacity "Meili" arm kneader: • Emulsion of the methoxy-functional oil (A) prepared above, 447 g and • 1.56 g of 37% dioctyltin dilaurate. After 15 minutes of kneading, 150 g of Socal 312
N "Introduce calcium carbonate. Again, kneading is carried out for 15 minutes, the mixture is degassed under vacuum and packed in a sealed cartridge. Table 1 shows the properties of the sealant.

Examples 6-9 The following aminosilanes were added to the aqueous dispersion: N-methyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Example 5 is repeated by adding 3 g each of N-aminoethyl-3-aminopropylmethyldimethoxysilane. The properties of the mixture in which the cartridge was stored are listed in Table 2.

Example 10 Preparation of a methoxy-functional oil (A) The procedure described in Example 5 is repeated using 45 g of vinyltrimethoxysilane instead of 15 g.

Preparation of an Emulsion of Silicone Phase (F) Consisting of a Methoxy-Functional Oil (A) To the obtained oil, add HLB = 11.7 g under the trade name “Cemulsol NP
150 g of "7" (nonylphenol containing 7 ethoxy units, marketed by Rhone Poulin).
Kneading is performed at 90 rpm for about 5 minutes, and then 160 g of water is
Add over 10 minutes and knead at 90 revolutions / minute for 90 minutes. The resulting emulsion has an average particle size of 1670nm. Then it is diluted by the addition of 390 g of water.

Preparation of Aqueous Dispersion and Water Sealant In a 1.6 liter capacity "Meili" arm kneader:-Emulsion of methoxy-functional oil (A) prepared above
465 g, and 1.56 g of dioctyltin dilaurate emulsion are introduced. After 15 minutes of stirring, 150 g of Socal 312
N "Calcium carbonate is introduced and kneading is carried out for 30 minutes. 3 g of N-methyl-3-aminopropyltrimethoxysilane are added. Stir for 30 minutes before applying vacuum and packaging into cartridges. Table 3 shows the properties of the obtained mixture.

Example 11 Preparation of an Emulsion of Silicone Phase (F) To the kneader of Example 1, 1525 g of "48V175000 oil" and 15 g of N-methyl-3-aminopropyltrimethoxysilane are introduced. The mixture is kneaded at 90 rpm for 20 minutes and then a slight vacuum is applied for 5 minutes. 70g of Cemulsol NP
Add a premix of 5 "and 70g of" Cemulsol NP 12 ". This surfactant mixture has an HLB of 11.4. 90
The kneading is carried out for 10 minutes at rpm / min, then 120 g of water are introduced under stirring over a period of about 7 minutes. At 90 rpm
Knead for 45 minutes. The resulting emulsion has an average particle size of 2400nm. Add 30g of water over about 3 minutes,
And if kneading is continued for 90 minutes under the same conditions, the particle size is 1790
nm. The emulsion is diluted with 400 g of water to have a solids content of 74%.

Preparation of Aqueous Dispersion and Water Sealant Into a 1.6 liter "Meili" arm kneader, introduce: 405 g of the emulsion prepared above, and 1.56 g of dioctyltin dilaurate emulsion. Mix for 15 minutes. 150g of Socal 312
N "calcium carbonate is introduced, kneading is performed for 30 minutes, degassed under vacuum and the mixture is packaged in cartridges.
The properties of the mixture are described in Table 3.

Example 12 Preparation of an emulsion of the silicone phase (F) To the kneader of Example 1, 1500 g of "48V175000 oil" and 45 g of vinyltrimethoxysilane are introduced. After stirring at 90 rpm for 5 minutes, 12 g of a methanol solution containing 3.75% lithium oxide are added. 90
Stirring is carried out for 20 minutes at rpm / min, and the mixture is then neutralized with the reaction product of 9 g of phosphoric acid and octamethyltetracyclosiloxane (containing 8.5% of phosphoric acid). After stirring for 15 minutes under the same conditions, the product is degassed under vacuum for 15 minutes.

Preparation of an emulsion of silicone phase (F) consisting of methoxy-functional oil (A) To the oil thus obtained, 75 g of "Cemulsol NP 5" and 75 g
Add the mixture of g with "Cemulsol NP 12". 90 rotations /
The kneading is carried out for 5 minutes per minute and then 130 g of water are introduced over a period of about 8 minutes. After kneading at 90 rpm for 90 minutes, an emulsion with an average particle size of 630 nm is obtained. Then add 420
Dilute it by adding g of water.

Preparation of Aqueous Dispersion and Water Sealant Into a 1.6 liter capacity "Meili" arm kneader: 453 g of the emulsion prepared above, and 1.56 g of dioctyltin dilaurate emulsion are introduced. Stir for 15 minutes, then 150 g of "Socal
312 N ”Introduce calcium carbonate. Mix for 30 minutes. Then 6 g of N-methyl-3-aminopropyltrimethoxysilane are added. The kneading is carried out for 30 minutes and the mixture is degassed under vacuum before packaging in cartridges. The properties of the mixture are described in Table 3. The pH of the dispersion is 8.

Example 13 Preparation of an Emulsion of Silicone Phase (F) In the kneader of Example 1, dispersed in 1500 g of "48V175000 oil", and 30 g of α, ω-bis (trimethyl) polydimethylsiloxane oil having a viscosity of 50 mPa s 3 g of dioctyltin dilaurate are introduced. This mixture is kneaded at 90 rpm for 15 minutes. Add 150 g of "Cemulsol NP 9" and stir for 90
Run for 15 minutes at rpm. Then 120 g of water are slowly poured in with stirring over a period of about 10 minutes, and the mixture is kneaded under stirring for 150 minutes. The resulting emulsion is 410 nm
Particle size. This is then diluted with 430 g of water to 75
% Solids content is obtained.

Preparation of Aqueous Dispersion and Water Sealant In a 1.6 liter capacity "Meili" arm kneader: 471 g of the emulsion prepared above; 210 g of calcium carbonate "Winnofil SP" (commercially available by ICI); Silicone as described in Example 1 21 g of DT and 10 g of a solution containing 50% of KOH are introduced continuously, and kneading is carried out for 30 minutes each after the introduction of each of the components of the mixture. The final dispersion is degassed under vacuum for 5 minutes and packaged in a sealed packaging material. The properties are described in Table 3.

Example 14 Preparation of an Emulsion of Silicone Phase (F) To the kneader of Example 1, 1500 g of "48V175000 oil" and 45 g of precipitated silica "FK 160" precipitated silica (commercially available from Degussa) are introduced. This mixture is kneaded at 70 rpm for 20 minutes.
Add 75 g of "Cemulsol NP 5" and 75 g of "Cemulsol NP 12". This mixture is kneaded at 70 rpm for 15 minutes.
Next, 150 g of water was gradually poured in over 10 minutes while stirring at 90 rpm, and kneading was continued for 150 minutes with the same stirring.
Do for a minute. The resulting emulsion has an average particle size of 440nm. It is then diluted with 400 g of water. A solids content of 76.2% is obtained.

Preparation of Aqueous Dispersion and Water Sealant In a 1.6 liter capacity "Meili" arm kneader: 447 g of the emulsion prepared above, 1.56 aqueous emulsion containing 37% dioctyltin dilaurate and stabilized with polyvinyl alcohol
g, "Winnofil SP" 150 g of calcium carbonate, 21 g of the silicone DT described in Example 1, and 10 g of a solution containing 50% of KOH, which are introduced continuously. After each introduction, kneading is performed for 30 minutes. The final dispersion is degassed under vacuum for 5 minutes and packaged in a sealed packaging material. The properties are described in Table 3.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 83/04-83/08

Claims (14)

(57) [Claims] 1. At least one organopolysiloxane oil (A) which can be crosslinked to an elastomer by condensation in the presence of a crosslinking agent (B), if necessary. 0.1 to 100 parts by weight of at least one crosslinking agent (B) per part by weight, as an optional component up to 50 parts by weight of at least one silane (C) per 100 parts by weight of oil (A), as an optional component An aqueous dispersion comprising up to 300 parts by weight of a siliceous and / or non-siliceous inorganic filler (D) per 100 parts by weight of oil (A), and a catalytically effective amount of a curing catalyst compound (E). A silicone phase (F) having a kinematic viscosity at 25 ° C. of at least 3 Pas, comprising an oil (A) or a mixture of oils (A) and optionally components (B), (C), ( A silicone phase containing at least one of D) and (E) ( ) And 100 parts by weight of at least one surfactant (G) (HLB of a mixture of such surface-active agents or surface active agent is at least 10)
3 to 20 parts by weight of water and 2 to 20 parts by weight of water, and the weight ratio of water / water + surfactant is such that the viscosity of the mixture of water + surfactant is the silicone phase (F). The mixture is such that it is about half or higher in viscosity of the oil / oil having a particle size of 0.1-5 μm.
Kneading for sufficient time and under shear conditions to obtain a "water-in-water" emulsion, then optionally diluting with water until a solids content of 25-97% is obtained; and-components not present in the silicone phase (F) An aqueous dispersion obtained by adding 2. The oil (A) wherein the oil (A) contains at least two functional groups per molecule which can optionally be condensed after hydrolysis.
The aqueous dispersion according to claim 1, which is a hydroxylated oil or a functional oil. 3. An oil (A) having the general formula (I) Wherein a is 0 or 1; b is 0 or 1; a + b = 0, 1 or 2, n is sufficient to give the polymer of formula (A) the desired viscosity. R groups are the same or different and OH groups (when a + b = 2) alkoxy or alkenyloxy groups containing 1 to 10 carbon atoms, 6 to 13 carbon atoms An aryloxy group containing 1 to 13 carbon atoms, an acyloxy group containing 1 to 13 carbon atoms, a ketiminoxy group containing 1 to 8 carbon atoms, 1 to 6 carbon atoms bonded to silicon by a Si-N bond. Wherein the R ¹ and R ² groups are the same or different and are an alkyl or alkenyl aliphatic group containing 1 to 10 carbon atoms or a phenyl aromatic group. And such a group is a halogen atom or a Optionally substituted by ano groups, at least 80% of which represent methyl groups; R ³ and R ⁴ groups being the same or different and containing 1 to 13 carbon atoms, alkyl, amino Represents an organic group which is an alkyl, polyaminoalkyl, epoxyalkyl or alkenyl aliphatic group or an arylaromatic containing from 6 to 13 carbon atoms, and optionally has at least two functional groups per molecule which can be condensed after hydrolysis. Is present]. 4. The crosslinking agent (B) is a colloidal silica, sodium silicate, pyrogenic or precipitated silica, alkali metal organosiliconate, microemulsion of silsesquioxane resin, low molecular weight containing alkoxy and acyloxy groups. A reactive silicone resin, a high molecular weight toluene-insoluble silicone resin, a hydroxylated silicone resin, an alkoxysilane, an alkylaminosilane, an alkylamidesilane or the like.
The aqueous dispersion according to any one of the above. 5. The silane (C) is a by-product of the hydrolysis of the oil (A) and has the formula (R ⁵ ) _c Si (R) _{4-c where} c is 0, 1 or 2 R ⁵ groups are the same or different and are of the oil (A) of formula (I)
R groups correspond to the groups R ³ and R ⁴ , wherein the R group is a polyorganosiloxane oil of formula (I) (A)
Wherein the silane is present in an amount of from 0 to 10 parts by weight per 100 parts by weight of the oil (A). Aqueous dispersion of 6. Aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, glycidoxypropyltrisilane, wherein the silane (C) is present in an amount which can range up to 50% by weight of the oil (A). The aqueous dispersion according to any one of claims 1 to 4, which is an additive for modifying adhesion such as methoxysilane. 7. A filler (D) for reinforcing or semi-reinforcing particles having a particle size of 0.001 to 300 μm.
The aqueous dispersion according to any one of the above. 8. The method according to claim 1, wherein the curing catalyst compound (E) is a tin derivative used in an amount which may be in the range of 3 parts by weight per 100 parts by weight of the oil (A). The aqueous dispersion according to any one of the above. 9. A mixture of (F1) an oil (A) having a viscosity of at least 3 Pa s, (F2) an oil (A) having a viscosity of at least 3 Pa s, (F3) at least 3 Pa s At least one having a viscosity of
A mixture of at least one oil (A) and at least one crosslinking agent (B) (if necessary) and / or a silane (C) and / or at least one filler (D), or (F4) optional components At least one silane (C) as
And / or a mixture of at least one oil (A) and a catalyst compound (E) in the presence of at least one filler (D). The aqueous dispersion according to the above item. 10. An "oil / water" emulsification of the silicone phase (A) is achieved by introducing the silicone phase into a water + surfactant mixture or by introducing water into the silicone phase + surfactant mixture. The aqueous dispersion according to any one of claims 1 to 9, wherein the dispersion is performed by kneading at a temperature of 10 to 50 ° C. 11. After the optional dilution of the mixture, the components of the dispersion that are not present in the "oil / water" emulsion of the silicone phase (A), namely the silicone phase (F1), (F2) or (F3) In the case of an emulsion, the catalyst compound and other optional components not present in the phase; in the case of an emulsion of the silicone phase (F4), the crosslinking agent (B) (if necessary) and other components not present in the phase. 11. The aqueous dispersion according to claim 10, wherein the optional component is introduced and dispersed in the mixture by kneading. 12. A kneading operation comprising the steps of:
Planetary mixer, hook mixer, slow death parser, static mixer or blade, propeller,
12. The aqueous dispersion according to claim 10, wherein the aqueous dispersion is performed with an anchor or a similar mixer. 13. The aqueous dispersion according to claim 1, further comprising a plasticizer, a thickener, and a filler-dispersant. 14. Use of the aqueous dispersion according to any one of claims 1 to 13 for producing an elastomer paint, a drug for imparting water repellency to a surface material, a sealing material, and a flame-retardant elastomer product. .